Electromethanogenesis reactor

ABSTRACT

Generation of energy and storage of energy for subsequent use is provided by electromethanogenesis of carbon dioxide into a fuel gas and the storage of the fuel gas for subsequent use. An electromethanogenic reactor includes an anode conductor and a cathode conductor wherein the cathode conductor includes submicron to micron scale pores. Electromethanogenesis microbes and/or enzymes are located in the micron scale pores of the cathode electrode conductor. Carbon dioxide is introduced into the electromethanogenic reactor and the electromethanogenesis microbes/enzymes and the carbon dioxide interact and produce a fuel gas. The fuel gas is stored for subsequent use, for example use in power generation.

STATEMENT AS TO RIGHTS TO APPLICATIONS MADE UNDER FEDERALLY SPONSOREDRESEARCH AND DEVELOPMENT

The United States Government has rights in this application pursuant toContract No. DE-AC52-07NA27344 between the United States Department ofEnergy and Lawrence Livermore National Security, LLC for the operationof Lawrence Livermore National Laboratory.

BACKGROUND Field of Endeavor

The present application relates to electromethanogenesis and moreparticularly to a electromethanogenesis reactor.

State of Technology

This section provides background information related to the presentdisclosure which is not necessarily prior art.

Electromethanogenesis is a form of electrofuel production where methaneis produced by direct biological conversion from electrical current andcarbon dioxide. Electromethanogenesis uses microbes adsorbed on planargraphite electrodes. The current density and consequently the volumetricproductivity of this design are limited by the electrode interfacialarea that is accessible to the microbes. Additionally, it is difficultto maintain the reactor geometry and density when scaling up of theseelectrode materials to large reactor sizes.

SUMMARY

Features and advantages of the disclosed apparatus, systems, and methodswill become apparent from the following description. Applicant isproviding this description, which includes drawings and examples ofspecific embodiments, to give a broad representation of the apparatus,systems, and methods. Various changes and modifications within thespirit and scope of the application will become apparent to thoseskilled in the art from this description and by practice of theapparatus, systems, and methods. The scope of the apparatus, systems,and methods is not intended to be limited to the particular formsdisclosed and the application covers all modifications, equivalents, andalternatives falling within the spirit and scope of the apparatus,systems, and methods as defined by the claims.

We are entering an era where energy from photovoltaics, wind, and otherrenewable sources is abundant and inexpensive during peak productionperiods. Technologies that can store this energy long term (e.g.seasonally) are highly desired. Storage as methane would allow Methaneto serve as an energy storage medium that can be stored or transportedusing mature technologies and immediately integrated into existinginfrastructure. Natural gas power plants emit fewer pollutants and aremore efficient than coal-fired power plants. Furthermore, for eachmethane molecule produced, a CO₂ molecule is consumed, reducing theclimate impacts of burning natural gas. Electromethanogenesis is themicrobial conversion of CO₂ to methane and has the potential to be lesscapital and energy intensive than chemical methods for this conversion(electrolysis followed by Sabetier process). However, to capitalize onthe efficiency of microbes, new reactor designs and electrode materialsare needed to increase current density and scalability.

The inventors' apparatus, systems, and methods provide the generation ofenergy and the storing of the energy for subsequent use by providingcarbon dioxide, electromethanogenesis of the carbon dioxide into a fuelgas, and the storing of the fuel gas for subsequent use. The inventors'apparatus, systems, and methods utilize an electromethanogenic reactorhaving an anode conductor and a cathode conductor wherein the cathodeconductor includes nanometer to micron scale pores.Electromethanogenesis microbes or enzymes are located in the micronscale pores of the cathode electrode conductor. Carbon dioxide isintroduced into the electromethanogenic reactor, wherein theelectromethanogenesis microbes or enzymes and the carbon dioxideinteract and produce a fuel gas. The fuel gas is stored for subsequentuse, for example use in power generation.

The inventors' apparatus, systems, and methods provide a scalable,production module for microbial methanogenesis of methane gas from CO₂.This inventors' apparatus, systems, and methods may also be used inother microbial electrosynthesis including production of other fuels orspecialty chemicals, such as hydrogen peroxide or acetate, from CO₂. Theinventors' apparatus, systems, and methods utilize 3D printed electrodematerials with adsorbed electromethanogenesis microbes or enzymes thathave tunable geometry, surface area, and surface chemistry to maximizecurrent density in microbial electromethanogenesis of CO₂ to methane ina modular reactor. Volumetric productivity scales with current density,therefore by tuning the surface area and microbe/enzyme adsorption thecurrent density can be optimized. The inventors' apparatus, systems, andmethods have use in energy storage, CO₂ mitigation, industrial biogasproduction, fuel synthesis, syngas, and other applications.

The inventors' apparatus, systems, and methods use 3D printed highsurface area electrode-based reactors with adsorbed microbes/enzymes forcharge transfer to overcome the limitations of microbialelectromethanogenesis. The inventors' apparatus, systems, and methodshave numerous benefits that include three unique aspects that aredesigned to increase charge transfer efficiency and reactor volumetricproductivity:

Aspect #1—This is the first use of graphene aerogels for microbialelectromethanogenesis, which allows the current density to be maximizeddue to the ability to control material pore size (and thus biologicallyaccessible surface area) over 4 orders of magnitude (1 nm to 10 μm) andconductivity from 1 to 100's of S/cm.

Aspect #2—The inventors' apparatus, systems, and methods use adsorbedenzymes to mediate charge transfer rather than whole microbial cultures.The use of enzymes to mediate charge transfer can increase currentdensity, since nanometer scale enzymes can access more electrode surfacearea than significantly larger micron scale whole microbes. Furthermore,using enzymes rather than microbes for the critical charge transfer stepallows a wider range of process conditions, e.g. temperatures and pH,which can be used to increase catalytic activity and CO₂ solubility.Separating the charge transfer from the methanogenesis step to achemical intermediate production step also allows a wider range ofmicrobial species that can be used for methanogenesis; processes formicrobial methane production from syngas have been optimized andestablished for industrial biogas production.

Aspect #3-3D printing these reactors maximizes volumetric productivityby both optimally utilizing 3D space and reducing diffusion limitations.Furthermore, 3D printed reactors allow for modular and flow-throughdesigns, positioning the technology for scale-up and commercialization.

The apparatus, systems, and methods are susceptible to modifications andalternative forms. Specific embodiments are shown by way of example. Itis to be understood that the apparatus, systems, and methods are notlimited to the particular forms disclosed. The apparatus, systems, andmethods cover all modifications, equivalents, and alternatives fallingwithin the spirit and scope of the application as defined by the claims.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings, which are incorporated into and constitute apart of the specification, illustrate specific embodiments of theapparatus, systems, and methods and, together with the generaldescription given above, and the detailed description of the specificembodiments, serve to explain the principles of the apparatus, systems,and methods.

FIG. 1 is a flow chart that illustrates a conceptual model for one ormore embodiments of the inventor's apparatus, systems, and methods.

FIG. 2A is a flow chart that illustrates and describes a number ofembodiments of the inventor's apparatus, systems, and methods.

FIG. 2B, is an illustration of a 3D printed cathode electrode of theinventor's apparatus, systems, and methods.

FIG. 2C illustrates an embodiment for 3D printing and otherwiseadditively manufacturing a cathode electrode of the inventor'sapparatus, systems, and methods.

FIG. 2D, illustrates a FIG. 2D a lattice like construction a cathodeelectrode of the inventor's apparatus, systems, and methods.

FIG. 2E shows the structural components of an embodiment of theinventors' bioreactor reactor for microbial electromethanogenesis.

FIG. 2F shows the inventors' bioreactor reactor with the addition of anenzyme broth into the reactor vessel.

FIG. 2G shows the inventors' bioreactor reactor with the enzyme broth inthe reactor vessel 228 and an electrical load 234 connected to thecathode 216 and conductors (cathode electrode conductor & anodeelectrode conductor) that provides a current with a direction ofcurrent.

FIG. 2H shows the bioreactor reactor with the enzyme broth in thereactor vessel, an electrical load connected to the cathode andconductors (cathode electrode conductor & anode electrode conductor),and the enzyme broth being drawn to the cathode.

FIG. 2I illustrates details of the 3D printed cathode electrode withadsorbed enzymes.

FIG. 2J shows the inventors' bioreactor reactor with the enzyme broth inthe reactor vessel, an electrical load connected to the cathode andconductors (cathode electrode conductor & anode electrode conductor),wherein the enzyme broth is drawn to the cathode and a storage facilityis connected to the reactor.

FIG. 2K shows the inventors' bioreactor reactor with the enzymes in thereactor vessel, an electrical load connected to the cathode andconductors (cathode electrode conductor & anode electrode conductor),wherein the enzymes are drawn to the cathode, a storage facility, and asystem for introducing carbon dioxide into the reactor vessel.

FIG. 3 illustrates an embodiment of the inventors' bioreactor reactorthat includes a 3D cathode reactor array for microbialelectromethanogenesis.

DETAILED DESCRIPTION OF SPECIFIC EMBODIMENTS

Referring to the drawings, to the following detailed description, and toincorporated materials, detailed information about the apparatus,systems, and methods is provided including the description of specificembodiments. The detailed description serves to explain the principlesof the apparatus, systems, and methods. The apparatus, systems, andmethods are susceptible to modifications and alternative forms. Theapplication is not limited to the particular forms disclosed. Theapplication covers all modifications, equivalents, and alternativesfalling within the spirit and scope of the apparatus, systems, andmethods as defined by the claims.

Referring now to the drawings, and in particular to FIG. 1, a conceptualmodel for one or more embodiments of the inventor's apparatus, systems,and methods is presented in a flow chart. The model and flow chart aredesignated generally by the reference numeral 100. The model and flowchart 100 include the components and steps listed below.

-   -   102—renewable energy source (example: wind/solar),    -   104—low cost electrons,    -   106—electrocatalyst,    -   108—fuel/chemicals,    -   110—manufacturing/transportation,    -   112—CO₂ emissions, and    -   114—recirculation of CO₂ from block 112 back to block 106.

The components and steps of the flow chart 100 having been identifiedand described, the conceptual model will be considered. The inventor'sapparatus, systems, and methods provide a scalable, intermediateproduction module for microbial methanogenesis from CO₂. The inventor'sapparatus, systems, and methods can also be used in other microbialelectrosynthesis including production of other fuels or specialtychemicals, such as hydrogen peroxide or acetate, from CO₂.

Renewable energy sources 102 are used to produce low cost electrons 104.An example is the use of solar cells 102 to produce low cost electrons104. Other sources of low cost electrons can be used. The low costelectrons 104 are used with electrocatalyst 106 to produce fuel and/orchemicals 108. The fuel and/or chemicals 108 are then used inmanufacturing and/or transportation 110. The manufacturing and/ortransportation 110 produces CO₂ emissions 112. The CO₂ emissions 112 arerecycled back to the electrocatalyst 106.

Referring now to FIG. 2A through FIG. 2J; numerous embodiments of theinventor's apparatus, systems, and methods are presented. In FIG. 2A aflow chart describes a number of embodiments of the inventor'sapparatus, systems, and methods. The embodiments and the flow chart aredesignated generally by the reference numeral 200. The embodiments andflow chart 200 include the components and steps listed below.

(202) Step 1—Select a material for use in the construction of anelectrode (cathode), maximum pore density is a desirable property,(material example: graphene aerogel); this step and component is furtherillustrated and described in FIG. 2B;

(204) Step 2—Using graphene aerogel ink 3D print the cathode structurewith maximum surface area being desirable; this step and component isfurther illustrated and described in FIG. 2C and FIG. 2D;

(206) Step 3—Install cathode in a reactor cell; this step and componentis further illustrated and described in FIG. 2E;

(208) Step 4—Fill reactor cell with enzyme broth; this step andcomponent is further illustrated and described in FIG. 2F;

(210) Step 5—Apply electrical load to the reactor cell; this step andcomponent is further illustrated and described in FIG. 2G;

(212) Step 6—The enzymes will migrate to the cathode and enter the poreswhere a chemical process will occur; this step and component is furtherillustrated and described in FIG. 2H and FIG. 2I;

(214) Step 7—The methane is the sequestered in a storage facility forfuture use; this step and component is further illustrated and describedin FIG. 2.

The embodiments and steps of the flow chart 200 having been identifiedand described, the embodiments of the inventor's apparatus, systems, andmethods will be considered. The embodiments of the inventor's apparatus,systems, and methods provide 3D printed electrode materials that havetunable geometry, surface area, and surface chemistry to maximizecurrent density, with adsorbed microbes/enzymes in microbialelectromethanogenesis of CO₂ to methane in a modular reactor. Volumetricproductivity scales with current density, therefore by tuning thesurface area and microbe/enzyme adsorption the current density can beempirically studied to achieve an output that cart theoretically achievevolumetric productivity of at least multiple g/L/hr. The use of 3Dprintable, high porosity resorcinol-formaldehyde aerogel as electrodematerial also enables unique, scalable reactor geometries and theflexibility of a batch or flow-through reactor design.

Current density scales with productivity because the current resultsonly from electrochemical reactions at the electrode interface at thelow (100's of millivolts) potentials applied. To increase currentdensity to a target of 0.1 Amps per m2, which at a target electroncapture efficiency of 80% will lead to a very high volumetricproductivity of 32 g CH₄/L cathode/hour (assuming a surface area of5×106 m2/m3 and 100% conversion of hydrogen and formate to methane) theelectrode interfacial area that is accessible to the enzymes must bemaximized. Surface area that is due to pore sizes smaller than themicrobes/enzymes/enzyme complexes does not contribute to increasecurrent density. In order to tune the pore size and conductivity of theelectrodes, the resorcinol to formaldehyde concentration of the materialmay be varied during synthesis.

In addition to surface area, the surface chemistry may be tuned tofacilitate microbe/enzyme adsorption and beneficial orientation (withthe redox active site oriented toward the electrode surface).Controlling surface charge, e.g. by introducing positively chargedgroups, or introducing transition metals (e.g. Ni nanoparticles) mayincrease adsorption to electrodes and therefore increase current densityand microbe/enzyme stability.

Current density is also controlled by the availability of protons (localpH) at the cathode, since protons are co-reactants in theelectrochemical reduction of CO₂. Protons are generated by oxidation ofwater at the anode and are typically supplied through a proton exchangemembrane such as Nafion, which also prevents O₂ transport to andnon-productive reduction at the cathode. The cathode and anode spacingmay be varied to optimize proton and O₂ transport, and an ion exchangemembrane may be printed onto the electrode to prevent O₂ transport andseparate O₂ from the H₂ product stream. However, the cathode and anodespacing may be designed such that small bubbles of pure CO₂ preventmigration of O₂. Unique designs only available to 3D printed or extrudedelectrode materials, such as coaxial tubes incorporating printed protonexchange membranes, or interdigitated layered electrodes, may be usedorder to maximize use of the reactor volume. The 3D printed,enzyme-adsorbed electrodes may be used in prototype reactor designs witheither batch processing or continuous flow.

The embodiments of the inventor's apparatus, systems, and methods use 3Dprinted high surface area electrode-based reactors with adsorbed enzymesfor charge transfer to overcome the limitations of microbialelectromethanogenesis. The inventor's apparatus, systems, and methodshave three unique aspects that are designed to increase charge transferefficiency and reactor volumetric productivity:

First, this is the first use of graphene aerogels for microbialelectromethanogenesis, which allows the current density to be maximizeddue to the ability to control material pore size (and thus biologicallyaccessible surface area) over 4 orders of magnitude (1 nm to 10 μm) andconductivity from 1 to 100's of S/cm.

Second, the inventor's apparatus, systems, and methods use adsorbedenzymes to mediate charge transfer rather than whole microbial cultures.The use of enzymes to mediate charge transfer can increase currentdensity, since nanometer scale enzymes can access more electrode surfacearea than significantly larger micron scale whole microbes. Furthermore,using enzymes rather than microbes for the critical charge transfer stepallows a wider range of process conditions, e.g. temperatures and pH,which can be used to increase catalytic activity and CO₂ solubility.Separating the charge transfer from the methanogenesis step to achemical intermediate production step also allows a wider range ofmicrobial species that can be used for methanogenesis; processes formicrobial methane production from syngas have been optimized andestablished for industrial biogas production.

Third, 3D printing these reactors maximizes volumetric productivity byboth optimally utilizing 3D space and reducing diffusion limitations.Furthermore, 3D printed reactors allow for modular and flow-throughdesigns, positioning the technology for scale-up and commercialization.

Referring now FIG. 2B, an embodiment of an electrode of the inventor'sapparatus, systems, and methods is illustrated. The electrode isdesignated generally by the reference numeral 116. The electrode 116 isa 3D printed cathode electrode constructed of materials that arecompatible with enzymes that are adsorbed or attached to the electrode.The materials for the construction of the cathode electrode 116 providemaximum pore density. The materials can be carbon with high porosity.For example, the materials can be carbon aerogel with high porosity. Anexample is graphene aerogel. In a preferred embodiment the materials areresorcinol-formaldehyde aerogel with high porosity. The 3D printedcathode electrode has a tunable geometry, surface area, and surfacechemistry to maximize current density in microbial electromethanogenesisof CO₂ to methane in a modular reactor. As shown in FIG. 2B the cathodeelectrode 216 includes pores 218. The pores 218 are sub-micron to micronscale pores that provide high surface area.

Referring now FIG. 2C, an embodiment that provides apparatus, systems,and methods for 3D printing and otherwise additively manufacturing acathode electrode 216 of the inventor's apparatus, systems, and methodsis illustrated.

As illustrated in FIG. 2C, extruded build material 220 is deposited on abuild platform 224 by print head 222. The extruded build material 220 iscomposed of materials that have tunable geometry, surface area, andsurface chemistry to maximize current density in microbialelectromethanogenesis of CO₂ to methane in a modular reactor. The printhead 222 has a nozzle for extruding the build material 220 onto thebuild platform 224. Movement of the print head 222 is controlled bycomputer controller 218 which provides freedom of movement along allaxes as indicated by the arrows 226. The specifications of the cathodeelectrode 216 product to be created by the system is fed to the computercontroller 218 with the widely used numerical control programminglanguage G-Code. The computer controller 218 uses the instructions tomove the print head 222 through a series of movements along the surface224 forming the cathode electrode 216 product. The materials for theconstruction of the cathode electrode 216 are materials that providemaximum pore density. An example is graphene aerogel. In a preferredembodiment the materials are resorcinol-formaldehyde aerogel with highporosity. The cathode electrode 216 includes pores that are sub-micronto micron scale pores that provide high surface area.

Referring now FIG. 2D, an embodiment of a 3D printed cathode electrode216 of the inventor's apparatus, systems, and methods is illustrated.The electrode 216 is a 3D printed cathode electrode constructed ofmaterials that are compatible with microbes or enzymes that are adsorbedor attached to the electrode. The materials for the construction of thecathode electrode 216 provide maximum pore density. The materials can becarbon with high porosity. For example, the materials can be carbonaerogel with high porosity. An example is graphene aerogel. In apreferred embodiment the materials are resorcinol-formaldehyde aerogelwith high porosity. The 3D printed cathode electrode has a tunablegeometry, surface area, and surface chemistry to maximize currentdensity in microbial electromethanogenesis of CO₂ to methane in amodular reactor. As shown in FIG. 2B the cathode electrode 216 includespores 218. The pores 218 are sub-micron to micron scale pores thatprovide high surface area. As illustrated in FIG. 2D, a lattice likeconstruction gives a large surface area. The materials for theconstruction of the cathode electrode 216 provide maximum pore density.

Referring now to FIG. 2E, structural components of an embodiment of theinventors' bioreactor reactor for microbial electromethanogenesis isillustrated. The bioreactor reactor is designated generally by thereference numeral 200. The bioreactor reactor 200 includes thecomponents listed below.

cathode 216,

reactor vessel 228,

conductors (cathode electrode conductor & anode electrode conductor)230.

The reactor vessel 238 houses cathode 216 and conductors (cathodeelectrode conductor & anode electrode conductor) 230. The cathode 216 isa 3D printed cathode electrode constructed of materials that will adsorbmicrobes or enzymes and that has tunable geometry, surface area, andsurface chemistry to maximize current density in microbialelectromethanogenesis of CO₂ to methane in the reactor 200. Thematerials used in the construction of the cathode electrode 116 providemaximum pore density. An example is graphene aerogel. The cathodeelectrode 116 includes pores that are sub-micron to micron scale poresthat provide high surface area.

Referring now to FIG. 2F, the bioreactor reactor 200 is shown with theaddition of an enzyme broth into the reactor vessel 228. The enzymebroth is represented by open circles 232. The reactor vessel 238 housescathode 216, conductors (cathode electrode conductor & anode electrodeconductor) 230, and enzyme broth 232.

Referring now to FIG. 2G, the bioreactor reactor 200 is shown with theenzyme broth 232 in the reactor vessel 228 and an electrical load 234connected to the cathode 216 and conductors (cathode electrode conductor& anode electrode conductor) 230. The load 234 provides a current with adirection of current 236 illustrated in FIG. 2G.

Referring now to FIG. 2H, the bioreactor reactor 200 is shown with theenzyme broth 232 in the reactor vessel 228, an electrical load 234connected to the cathode 216 and conductors (cathode electrode conductor& anode electrode conductor) 230, and the enzyme broth 232 being drawnto the cathode 216. The current 236 draws the enzyme broth 232 to thecathode 216.

Referring now FIG. 2I, details of the cathode electrode 216 areillustrated. The electrode 216 is a 3D printed cathode electrodeconstructed of materials that have tunable geometry, surface area, andsurface chemistry to maximize current density in microbialelectromethanogenesis of CO₂ to methane with adsorbed enzymes 232 in amodular reactor. The materials for the construction of the cathodeelectrode 216 provide maximum pore density. The cathode electrode 216includes pores 218. The pores 218 are submicron to micron scale poresthat provide high surface area. The enzymes 232 are linked to thecathode electrode 216 in the pores 218. The materials can be carbon withhigh porosity. For example, the materials can be carbon aerogel withhigh porosity. An example is graphene aerogel. In a preferred embodimentthe materials are resorcinol-formaldehyde aerogel with high porosity.The 3D printed cathode electrode has a tunable geometry, surface area,and surface chemistry to maximize current density in microbialelectromethanogenesis of CO₂ to methane.

Referring now to FIG. 2J, the bioreactor reactor 200 is shown with theenzyme broth 232 in the reactor vessel 228, an electrical load 234connected to the cathode 216 and conductors (cathode electrode conductor& anode electrode conductor) 230, the enzyme broth 232 drawn to thecathode 216, and storage facility 240. The bioreactor reactor 200produce methane and the methane is collected in the storage facility240.

Referring now to FIG. 2K, the bioreactor reactor 200 is shown with theenzymes 232 in the reactor vessel 228, an electrical load 234 connectedto the cathode 216 and conductors (cathode electrode conductor & anodeelectrode conductor) 230, storage facility 240, and CO₂ 242 beingintroduced into the enclosure 228. The CO₂ and the enzymes 232 producemethane in the bioreactor reactor 200 and the methane is collected inthe storage facility 240.

Referring again to FIGS. 2E through 2K, details and the operation of theinventors' bioreactor reactor 200 for microbial electromethanogenesiswill be described. The bioreactor reactor includes the components listedbelow.

electrodes (cathode electrode & anode electrode) 230,

reactor vessel 228,

cathode 216,

enzyme broth (the enzymes are represented by open circles) 232,

load 234,

direction of current 236,

migrating enzymes 238, and

storage facility 240.

We are entering an era where energy from photovoltaics and otherrenewable sources is abundant and inexpensive during peak productionperiods. Therefore, technologies that can store this abundant energylong term are highly desired. Recently, it was discovered that certainmicrobes are capable of converting electrical current and carbon dioxideinto fuels such as methane. The net reaction for electromethanogenesisis similar to that of photosynthesis, when solar energy is used as asource of electrons:

CO₂+8H+8e ⁻→CH₄+2H₂O  [Equation 1]

However, if the electrons are harvested from photovoltaic panels, theartificial photosynthesis afforded by microbial electromethanogenesis(ME) is about 100 times more efficient than terrestrial bioenergy cropsat harvesting solar energy. Additionally, ME does not require arableland, and can lead to a pure product stream, circumventing thedownstream processing challenges currently encountered in convertingdedicated bioenergy crops to fuels. The electron capture efficiency inME is typically around 90%, and the overall energy efficiency from CO₂to methane around 80%. While microbial electrosynthesis is being pursuedfor conversion of electrical energy and CO₂ to fuels or chemicals suchas hydrogen peroxide or acetate, the production of methane has specificadvantages: Methane can serve as an energy storage medium that can bestored or transported using mature technologies and immediatelyintegrated into existing infrastructure. Natural gas power plants emitfewer pollutants and are more efficient than coal-fired power plants.Furthermore, in this scheme, for each methane molecule produced, a CO₂molecule is consumed, reducing the climate impacts of burning naturalgas.

Both biological and materials/reactor design challenges must be overcometo commercialize the ME process. The inventors will focus onbreakthroughs in reactor design that the inventors can achieve givenrecent advances in the additive manufacturing of high surface areacarbon materials. The fundamentals of ME, specifically the electrontransfer mechanism between the cathode and the microbe, are not wellunderstood and are an active area of research. However, optimizing thisinterface, and thus the charge transfer, between the material and themicrobe, and scaling the materials for optimal use of the bioreactorvolume are critical toward creating a practical, scalable reactor.Because of this lack of understanding, research into optimizing thematerials interface, i.e. the surface chemistry to enhance chargetransfer, must be empirical.

Other desired aspects of the reactor design can be anticipated fromassessments of the path to commercialization of bioenergy crops andmicrobial fuel cells: first, to minimize capital costs, high volumetricproduction rates of at least multiple g/L/hr are necessary. Highvolumetric productivity, several orders of magnitude higher than thistarget, can theoretically be achieved with the high current density,measured in A/m², high coulombic efficiency (utilization of this currentby the microbe or adsorbed enzymes), and the high accessible electrodesurface area materials synthesized at LLNL, up to 500×10⁶ m²/m³.Additionally, a decade of research on microbial fuel cells (whichgenerate current from the biological oxidation of organics inwastewater) teaches us that electrode materials are desired which havehigh accessible surface area, are not prone to biofouling, and show highconductivity, and high stability. The inventors also learn from thelessons of microbial fuel cells in terms of challenges that have beenencountered in scaleup and industrial implementation: “the maindifficulty is not an intrinsic loss of power at scales but maintainingreactor geometry relative to electrode configurations and densities aslarger reactors are built . . . ”. This observation implies thatscale-up can be achieved if modular designs are implemented and provenat smaller scales. These requirements of 1) high surface area 2) highlyconductive electrodes built into 3) modular reactors which optimallydeliver high current densities in three-dimensional space can be metusing LLNL 3D printed electrode materials. In fact, LLNL routinely 3Dprints electrode materials which have comparable conductivity, but 100fold higher surface areas than what has been used previously in ME. Theability to print these materials into limitless geometries and modularreactors adds another key benefit: scalable reactors can be constructedwhich potentially do not require membranes, which reduce or eliminateproton and CO₂ diffusion limitations, which optimize use of threedimensional space, and thus the volumetric productivity of the reactor,and finally which enable continuous production of products in aflow-through design.

The present invention is further described and illustrated by examplesof apparatus, systems, and methods constructed in accordance with thepresent invention. Various changes and modifications of these exampleswill be apparent to those skilled in the art from the description of theexamples and by practice of the invention. The scope of the invention isnot intended to be limited to the particular examples disclosed and theinvention covers all modifications, equivalents, and alternativesfalling within the spirit and scope of the invention as defined by theclaims.

3D Printing of ARF (Acid-Catalyzed Resorcinol-Formaldehyde) Aerogel

A suspension of 3 g of water, 3.4 g of formaldehyde (F) (37% solution)and 6 wt % of cellulose was prepared by ultra-sonication for 24 h. Aftersonication and prior printing, 2.46 g of resorcinol (R) and 88 μL ofacetic acid (catalyst (C)) were added to the suspension. Thiscombination of R/F molar ratio of 1:2 and R/C molar ratio of 1:15,yielded a RF mass ratio of 42 wt %. After the addition of resorcinol,the 6 wt % of cellulose drops to 4 wt % in the overall suspension. Theoverall suspension is mixed for 5 min at 2000 rpm in a Thinky mixtureuntil a through mixing of resorcinol with formaldehyde/water/cellulosesuspension was obtained. However, for direct ink writing a thixotropicink is necessary with elastic stiffness such that the extruded beadsfrom the nozzle can span easily. To achieve the required stiffness inthe inks, 9 wt % of Fumed silica was mixed to the suspension and wasthen loaded to a syringe barrel for printing. The ink is then loadedinto a syringe barrel and centrifuged for a minute at 4000 rpm to removeair bubbles, after which the ink is extruded through a micro nozzle (600μm or 250 μm diameter) to pattern 3D structures. The patterns wereprinted on a glass substrate coated with PTFE spray. Simple cubiclattices with multiple orthogonal layers of parallel cylindrical rodswere printed alternately. The diameter of the cylindrical rods equalsthe diameter of nozzle and the center-to-center rod spacing of 1.2 mm(for 600 μm nozzle) and 0.8 mm (250 μm nozzle) were respectively used. Atotal of 10 layers were stacked on the structure such that each layerhas a z spacing of 0.3 mm. In order to avoid cracking due to evaporationof water, drops of iso-octane (2,2,4-trimethyl-pentane) was added ontothe printed structure frequently. The printed parts on the glasssubstrate is carefully placed in a container with iso-octane and sealedtightly to avoid evaporation of the solvent and are placed in the ovenat 80° C. for 72 h for gelation. Once gelled, the aqueous solvent (waterin this case) is removed by soaking the sample in an acetone bath for 3days. Note that the solvent needs to be exchanged every 24 h. This stepis crucial as the following procedure of super critical drying iscarried out with CO₂. The samples are then super critically dried inliquid CO₂ at a critical temperature of 55° C. and at a pressure rangeof 1200-1400 psi.

Carbonization and Activation of 3D Printed ARF Aerogel

This process involves carbonizing the supercritically dried 3D printedARF organic gel to form carbon aerogels. The aerogels were subjected toa heat treatment process where the samples were heated in a tube furnaceunder nitrogen atmosphere at 1050° C. for 3 h with a heating and coolingrate of 2° C./min. The carbonized 3D printed CAs were then etched withhydrofluoric acid to remove fumed silica. The etched parts were againsubjected to a three-day solvent (acetone) exchange followed by supercritical drying. For activation, the samples are now exposed to anoxidizing atmosphere at 950° C.

Referring now to FIG. 3, structural components of a 3D cathode reactorarray for microbial electromethanogenesis is illustrated. The 3D cathodereactor array is designated generally by the reference numeral 300. The3D cathode reactor array 300 includes the components listed below.

reactor housing (non-conducting) 302,

electrical isolators 304,

conductors (anode) 306,

3D cathodes 308,

enzyme broth 310.

load 312, and

product storage 314.

The reactor housing 302 houses electrical isolators 304, conductors(anode) 306, and 3D cathodes 308, and enzyme broth 310. The 3D cathodes308 are 3D printed cathode electrodes constructed of materials that willadsorbed enzymes and that has tunable geometry, surface area, andsurface chemistry to maximize current density in microbialelectromethanogenesis of CO₂ to methane in the reactor 300. Thematerials used in the construction of the 3D cathodes 308 providemaximum pore density. An example is graphene aerogel. The 3D cathodes308 include pores that are submicron to micron scale pores that providehigh surface area. The reactor 300 provides ganged 3D cathodes 308 toincrease the output of the reactor 300.

Although the description above contains many details and specifics,these should not be construed as limiting the scope of the applicationbut as merely providing illustrations of some of the presently preferredembodiments of the apparatus, systems, and methods. Otherimplementations, enhancements and variations can be made based on whatis described and illustrated in this patent document. The features ofthe embodiments described herein may be combined in all possiblecombinations of methods, apparatus, modules, systems, and computerprogram products. Certain features that are described in this patentdocument in the context of separate embodiments can also be implementedin combination in a single embodiment. Conversely, various features thatare described in the context of a single embodiment can also beimplemented in multiple embodiments separately or in any suitablesubcombination. Moreover, although features may be described above asacting in certain combinations and even initially claimed as such, oneor more features from a claimed combination can in some cases be excisedfrom the combination, and the claimed combination may be directed to asubcombination or variation of a subcombination. Similarly, whileoperations are depicted in the drawings in a particular order, thisshould not be understood as requiring that such operations be performedin the particular order shown or in sequential order, or that allillustrated operations be performed, to achieve desirable results.Moreover, the separation of various system components in the embodimentsdescribed above should not be understood as requiring such separation inall embodiments.

Therefore, it will be appreciated that the scope of the presentapplication fully encompasses other embodiments which may become obviousto those skilled in the art. In the claims, reference to an element inthe singular is not intended to mean “one and only one” unlessexplicitly so stated, but rather “one or more.” All structural andfunctional equivalents to the elements of the above-described preferredembodiment that are known to those of ordinary skill in the art areexpressly incorporated herein by reference and are intended to beencompassed by the present claims. Moreover, it is not necessary for adevice to address each and every problem sought to be solved by thepresent apparatus, systems, and methods, for it to be encompassed by thepresent claims. Furthermore, no element or component in the presentdisclosure is intended to be dedicated to the public regardless ofwhether the element or component is explicitly recited in the claims. Noclaim element herein is to be construed under the provisions of 35U.S.C. 112, sixth paragraph, unless the element is expressly recitedusing the phrase “means for.”

While the apparatus, systems, and methods may be susceptible to variousmodifications and alternative forms, specific embodiments have beenshown by way of example in the drawings and have been described indetail herein. However, it should be understood that the application isnot intended to be limited to the particular forms disclosed. Rather,the application is to cover all modifications, equivalents, andalternatives falling within the spirit and scope of the application asdefined by the following appended claims.

1. An apparatus for generating energy and storing the energy forsubsequent use, comprising: an electromethanogenesis reactor, an anodeelectrode conductor in said reactor, a cathode electrode conductor insaid reactor, submicron to micron scale pores in said cathode electrodeconductor, electromethanogenesis enzymes in said submicron to micronscale pores in said cathode electrode conductor, electromethanogenesismicrobes in said submicron to micron scale pores in said cathodeelectrode conductor, a system for introducing carbon dioxide into saidreactor, a voltage system for applying a voltage to said anode electrodeconductor and said second cathode electrode conductor wherein fuel gasis produced in said reactor, and a storage system for storing said fuelgas for subsequent use.
 2. The apparatus for generating energy andstoring the energy for subsequent use of claim 1 wherein said cathodeelectrode conductor is a graphene aerogel cathode electrode conductor.3. The apparatus for generating energy and storing the energy forsubsequent use of claim 1 wherein said cathode electrode conductor is aresorcinol-formaldehyde aerogel cathode electrode conductor.
 4. Theapparatus for generating energy and storing the energy for subsequentuse of claim 1 wherein said cathode electrode conductor is a 3D printedcathode electrode conductor.
 5. The apparatus for generating energy andstoring the energy for subsequent use of claim 1 wherein said cathodeelectrode conductor is a 3D printed cathode electrode conductor having athickness that is greater than the thickness of standard electrodes. 6.The apparatus for generating energy and storing the energy forsubsequent use of claim 1 wherein said cathode electrode conductor is a3D printed cathode electrode conductor having a surface and pores thatextend from said surface into said 3D printed cathode electrodeconductor.
 7. The apparatus for generating energy and storing the energyfor subsequent use of claim 1 wherein said voltage system providescurrent density in said cathode electrode conductor and wherein saidsubmicron to micron scale pores in said cathode electrode conductor,said electromethanogenesis enzymes, and said electromethanogenesismicrobes are selected to provide maximum current density in said cathodeelectrode conductor.
 8. The apparatus for generating energy and storingthe energy for subsequent use of claim 1 wherein saidelectromethanogenesis enzymes in said submicron to micron scale pores insaid cathode electrode conductor, said electromethanogenesis microbes insaid submicron to micron scale pores in said cathode electrodeconductor, said system for introducing carbon dioxide into said reactor,and said voltage system for applying a voltage to said anode electrodeconductor and said second cathode electrode conductor produces methanegas in said reactor
 9. A reactor apparatus for electromethanogenesis ofcarbon dioxide to methane, comprising: an electromethanogenesis reactorhousing, an anode electrode conductor in said electromethanogenesisreactor housing; a cathode electrode conductor in saidelectromethanogenesis reactor housing, said cathode electrode conductorhaving submicron to micron scale pores; electromethanogenesis enzymes insaid submicron to micron scale pores in said cathode electrodeconductor, electromethanogenesis microbes in said submicron to micronscale pores in said cathode electrode conductor, a system forintroducing carbon dioxide into said electromethanogenesis reactorhousing; and a voltage system for applying a voltage to said anodeelectrode conductor and said cathode electrode conductor wherein methaneis produced in said electromethanogenesis reactor housing.
 10. Thereactor apparatus for electromethanogenesis of carbon dioxide to methaneof claim 9 wherein said cathode electrode conductor is a 3D printedcathode electrode conductor.
 11. The reactor apparatus forelectromethanogenesis of carbon dioxide to methane of claim 9 whereinsaid cathode electrode conductor is a 3D printed cathode electrodeconductor having a thickness that is greater than the thickness ofstandard electrodes.
 12. The reactor apparatus for electromethanogenesisof carbon dioxide to methane of claim 9 wherein said cathode electrodeconductor is a 3D printed cathode electrode conductor having a surfaceand pores that extend from said surface into said 3D printed cathodeelectrode conductor.
 13. The reactor apparatus for electromethanogenesisof carbon dioxide to methane of claim 9 wherein said cathode electrodeconductor is a graphene aerogel cathode electrode conductor.
 14. Thereactor apparatus for electromethanogenesis of carbon dioxide to methaneof claim 9 wherein said cathode electrode conductor is aresorcinol-formaldehyde aerogel cathode electrode conductor.
 15. Amethod of generating energy and storing the energy for subsequent use,comprising the steps of: providing carbon dioxide, electromethanogenesisof said carbon dioxide into a fuel gas, and storing said fuel gas forsubsequent use.
 16. The method of generating energy and storing theenergy for subsequent use of claim 15 wherein said electromethanogenesisof said carbon dioxide into a fuel gas comprises electromethanogenesisof said carbon dioxide into methane gas.
 17. The method of generatingenergy and storing the energy for subsequent use of claim 15 whereinsaid electromethanogenesis of said carbon dioxide into a fuel gascomprises electromethanogenesis of said carbon dioxide into syngas. 18.The method of generating energy and storing the energy for subsequentuse of claim 15 wherein said step of storing said fuel gas forsubsequent use comprises using said fuel gas for power generation.
 19. Amethod of electromethanogenesis of carbon dioxide to methane, comprisingthe steps of: providing an electromethanogenesis reactor housing,providing an anode electrode conductor in said electromethanogenesisreactor housing; providing a cathode electrode conductor in saidelectromethanogenesis reactor housing, said cathode electrode conductorhaving submicron to micron scale pores; providing electromethanogenesisenzymes in said submicron to micron scale pores in said cathodeelectrode conductor, providing electromethanogenesis microbes in saidsubmicron to micron scale pores in said cathode electrode conductor,providing a system for introducing carbon dioxide into saidelectromethanogenesis reactor housing; and providing a voltage systemfor applying a voltage to said anode electrode conductor and saidcathode electrode conductor wherein methane is produced in saidelectromethanogenesis reactor housing.
 20. The method ofelectromethanogenesis of carbon dioxide to methane of claim 19 furthercomprising the step of selecting said electromethanogenesis enzymes andsaid electromethanogenesis microbes to provide maximum current densityin said cathode electrode conductor.
 21. The method ofelectromethanogenesis of carbon dioxide to methane of claim 19 whereinsaid step of providing a cathode electrode conductor in saidelectromethanogenesis reactor housing, said cathode electrode conductorhaving submicron to micron scale pores comprises providing a 3D printedcathode electrode conductor having a thickness that is greater than thethickness of standard electrodes.
 22. The method ofelectromethanogenesis of carbon dioxide to methane of claim 19 whereinsaid step of providing a cathode electrode conductor in saidelectromethanogenesis reactor housing, said cathode electrode conductorhaving submicron to micron scale pores comprises providing a 3D printedgraphene aerogel cathode electrode conductor.
 23. The method ofelectromethanogenesis of carbon dioxide to methane of claim 19 whereinsaid step of providing a cathode electrode conductor in saidelectromethanogenesis reactor housing, said cathode electrode conductorhaving submicron to micron scale pores comprises providing a 3D printedresorcinol-formaldehyde aerogel cathode electrode conductor.